N, n, n&#39;, n&#39;-tetrasubstituted diamines



United States Patent N,N,N,N-TETRASUBSTITUTED DIAMINES Delbert D.Reynolds and Thomas T. M. Laakso, Rochester, N. Y., assignors to EastmanKodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing.Application April 19, 1950, Serial No. 156,934

7 Claims. (Cl. 260-5705) This invention relates toN,N,N',N'-tetrasubstituted diamines and to a process for theirpreparation.

Various methods have been proposed heretofore for the preparation oftetrasubstituted diamines. For example, Freund et al., in Berichte derDeutsch. Chem., vol. 30, page 1385 (1897), proposed the preparation ofN,N,N',N'- tetramethyl ethylene diamine by heating ethylene bromide withdimethylamine in a closed tube at 100 C., while Knorr et al., ibid, vol.39, page 1428 (1906), proposed the preparation of N,N,N,N'-tetramethyltrimethylene diamine by heating trimethylene bromide with alcoholicdimethylamine at 150 C. More recently, Gilman and Pickens, in J. Amer.Chem. 800., vol. 47, pages 245-54 (1925), have described the preparationof N,N,N',N'- tetraethyl ethylene diamine by boiling a mixture offi-chloroethylbenzene sulfonate and diethylamine. However, the prior artprocesses have given relatively low yields and the intermediates forpreparing tetrasubstituted diamines with longer carbon chains are notreadily available.

We have now found that tetrasubstituted diamines having the generalformulas:

GEE-CH2 X CH2-CH2 wherein n represents a positive integer of from 2 to6, each R can be the same or difierent members selected from the groupconsisting of an alkyl group containing from 1 to 18 carbon atoms (e. g.methyl, ethyl, isopropyl, propyl, n-butyl, isobutyl, sec. butyl, tert.butyl, etc. groups), a cycloalkyl group containing from 5 to 6 carbonatoms (e. g. cyclopentyl or cyclohexyl groups), an aryl group (e. g.phenyl, p-tolyl, o-tolyl, etc.) or an aralkyl group (e. g. benzyl,phenylethyl, etc. groups) and X represents CH2 or O, can be prepared ina convenient and economic was by reacting a glycol disulfonate with asecondary amine and separating the tetrasubstituted diamine which forms.The above-defined diamines are useful as intermediates in thepreparation of other organic compounds, for example, in the preparationof quaternized polymeric sulfonates which are applicable as mordants incertain photographic color processes. They are also valuable in thepreparation of various insecticides and as pharmaceutical chemicals.

It is, accordingly, an object of the invention to provide a convenientand economic way for obtaining tetrasubstituted diamines. Another objectis to provide a 2,716,134 Patented Aug. 23, 1955 series of newtetrasubstituted diamines. will become apparent hereinafter.

In accordance with our invention, glycol disulfonates having the generalformulas:

Other objects wherein each R can be the same or different groups aspreviously mentioned, distilling olf the excess amine, if desired, afterthe reaction is completed, adding an excess of an aqueous alkali metalhydroxide (e. g. sodium, potassium or lithium hydroxide), separating theoil layer which thereupon forms and recovering the tetrasubstituteddiamine by fractional distillation of the oil layer. Advantageously thewater layer can be extracted with a water-insoluble solvent such asbenzene, diethyl ether, etc. in which case, the oil layer and theextract are combined and dried over a dehydrating agent such as sodiumhydroxide pellets, anhydrous potassium carbonate, etc., and thenfractionally distilled. For maximum yields, it is essential that thereactants be thoroughly dried and reacted under strictly anhydrousconditions. Advantageously, an inert solvent such as dry benzene,1,4-dioxane, toluene or xylene is employed as the reaction medium wherethe reactants are not readily compatible with one another. The amount ofthe secondary amine employed in the reaction can be varied widely from 4to 25 mol weights of the amine to each mol Weight of the glycoldisulfonate, but for the most efficient operation from 15 to 20 molweights of the amine are used for each mol weight of the glycoldisulfonate. The excess of the amine can be recovered and used insucceeding runs or recycled in continuous operation. The temperature ofthe reaction can vary from 50 to 150 C., but preferably it is conductedat the temperature corresponding to the refluxing or boiling temperatureof the amine or of the inert solvent medium or their mixtures. Thecaustic alkali employed to neutralize the reaction mixture, after thereaction has been completed, can be varied from just enough causticalkali to neutralize all of the acid groups released in the reaction andto free the tetrasubstituted amine from its salts, that is, from 2 to 15mol weights of the caustic alkali to each mol weight of the glycoldisulfonate, but preferably from 5 to 10 mol weights of the causticalkali to each mol weight of the glycol disulfonate. Advantageously, anaqueous solution of the caustic alkali is employed. Where an inertsolvent is employed as the reaction medium, the total concentration ofreactants can vary within any practical limits, it being possible tooperate at concentrations which contain as low as 10% and as high as ofreactants.

Suitable secondary amines which can be employed in the practice of ourinvention are dialkylamines such as dimethylamine, diethylamine,diisopropylamine, di-npropylamine, di-n-butylamine, dihexylamine,didodecylamine, distearylarnine, etc., mixed dialkylamines such asmethylethylamine, methyl propylamine, methylisopropylamine, methyln-butylarnine, ethyl propylamine, ethyl n-butylamine, methyldodecylamine, etc., diarylamines such as diphenylamine, di-p-tolylamine,etc., diaralkylamines such as dibenzylamine, di-ethylphenylamine, etc.

and dicycloalkylamines such as dicyclophentylamine, di-

'3 cyclohexylamine, etc. Suitable glycol disulfonates can be prepared bycondensing the appropriate sulfonyl chloride with the alkylene glycol orwith diethylene glycol as illustrated hereinafter. Among such suitableglycol di- 4 residual oil having a boiling point of 89/ 31.5 mm. Theyield of product was 40 g. equivalent to 79.5% of theory.

ANALYSIS sulfonates are l,2 di(methanesulfonoxy) ethane, l,2 -di- 5 F dCalm '(ethanesulfonoxy) ethane! l,3-di(methanesulfonoxy) lated propane,1,4 di (methanesulfonoxy) butane, 1,5 di

(methanesulfonoxy) pentane, 2,5-di(methanesulfonoxy) C PergtangPsrcgnoto hexane, l,2-di(benzenesulfonoxy) ethane, l,3-di(benzene j""""'sulfonoxy) propane, l,4-di(benzenesulfonoxy) butane, 10 16-7 16.7l,2-di(ptoluenesulfonoxy) ethane, 1,3-di(p-toluenesul- P Y) p an V (p'y) butane, Example 2.-N,N,N,N'-tetraisopropyl trimethylene ,B ,p'di(benzene sulfonoxy) diethyl ether, etc. I diamine Thefollowingexamples will serve further to illustrate the tetrasubstit uted'diamines of the. invention and the 606 (6 mol) of dnsopmpylamme and 115(032 manner of preparing the same.

PREPARATION OF GLYCOL DISULFONATES method. Otherglycol disulfonates canbe'prepared in similar manner by selecting the desired sulfonylchloride. In the table, the first column shows the glycol which isreacted with the appropriate sulfonyl chloride to give the glycoldisulfonate corresponding thereto and shown in the second column, whilethe other columns show the melting points, analyses and yields of therespective sulfonate derivatives.

mol) of anhydrous l,3-di(benzenesulfonoxy) propane were placed in a2-liter flask equipped with a calcium chloride vent tube, a 'variabletake-0E still head and a receiver, and the mixture refluxed for '20hours. Most of the amine (excess) .was distilled ofi, 56 g.of'potassiutn hydroxide dissolved in 300 cc.fof water was added andthemixture warmed until all of the solids went intosolution. 300 cc. ofbenzene were then added, and the benzene. layerlwhich separated wasdried over 40 g. of potassium hydroxide pellets and distilled through afractionating .column. There were obtained g. of N,N,N',N-tetraisopropyltrimethylene diamine, equivalent to 85.7% of theory, having a boilingpoint of 83/ 0.25 mm- ANALYSIS TABLE Analysis v Glycol SulfonateDerivative M. P., 0. 11.2 31

Caled Found 0, 49. 2 49. 4 Ethylene glycoLL. 1,2-Di-(benzenesu1fonoxy)ethane 48-50 1%, 64- 7 015312 5219 Propane-1,3 dio1'1,3-Di-(p-toluenesulfonoxy) propane 92-93 IESI, 69. 4

' 015413 54I3 Butane-1,4-diol lA Di-p-toluenesulfonoxy) butane 81-82Isl, 1g. 1?. g 67.0

013214 3213 Pentane-LE-diol 1,5-Di-(methanesulfonoxy) pentane; 35-36 H6.1 6. 1 82. 7

. S, 24. 6 24. 2 v C, 54. 3 54. 2 Hexane-2,5-diol2,5-Di-(benzenesulfonoxy) hexane 104-105 1%, g; i 73.7

01 49I 7 4916 Diethylene glycol fi,B-Di-(benzenesulfonoxy) diethylether. 38-39 HS, 14.6 66. 1

0, 54. 3 54. 6 Butane-1,3-diol 1,3-Di-(p-toluenesulionoxy) butane 58-5912st, 77. 0

Example 1.N,N,N,N tetraethyl. ethylene diamine 400 g. (5.48 mol) ofdiethylamine were boiled under 6 refluxand 100 g. (0.29 mol) ofl,2-di(benzenesulfonoxy) ethane. in 200 g; of dry dioxane were addedover a period of 4 hours. Most .of the amine (excess) was then distilledoil and 60 g. of sodium hydroxide pellets in 300 Example3.1,3-(diisopropylamino) butane 606 g. (6 mol) of diisopropylamine and1133 g. (0.33 mol) of 1,3-di (p-toluenesulfonoxy) butane were placed ina 2 liter, Z-necked flask, equipped with an 18 packed column, a variabletake-off still head and protected from moisture with a calcium chloridetube, and refluxed for 20 cc. of water added. The distillation was thencontinued hours" excess of diisopropylamine'was distilled to atemperature of from 93 'to 95 0, when the reactionnn'xture was cooledand extracted with three times its volume'of diethyl ether. The etherextract was dried over anhydrous potassium carbonate, filtered andconcentrated. The concentrate was then fractionated to give a 7 40 g. ofsodium hydroxide dissolved in 600 cc. of water was added to the mixture,followed by the addition of 1 liter of benzene; The benzene layer wasthen extracted with aqueous 5 hydrochloric acid, and the acid extract 5then made alkaline by the addition of suflicient aqueous 33% sodiumhydroxide solutioi The alkaline solution was extracted with 2 liters ofbenzene, the extract dried over sodium hydroxide pellets and the benzenethen removed by distillation of the mixture. The residual oil wasdistilled through a column using a variable still head take-off, to givea yield of 65% of theory of 1,3-(diisopropylarnino) butane having aboiling point of 85-87 C./ 1 mm.

Example 4.N,N,N',N-tetra-n-butyl tetramethylene diamine 600 g. (4.64mol) of di-n-butylamine and 100 g. (0.25 mol) of 1,4-di(p-toluenesulfonoxy) butane were refluxed for hours in an apparatussimilar to that described in Example 3. The excess of di-n-butylaminewas removed by distillation and 56 g. of potassium hydroxide in 300 cc.of water were added to the residual mixture. The oily layer whichseparated was drawn off, the aqueous layer extracted three times with300 cc. of benzene and combined with the drawn-oil oil. The combinedmaterial was dried over sodium hydroxide pellets and fractionallydistilled. The N,N,N,N-tetra-n-butyl tetramethylene diamine was obtainedas a light yellow oil boiling at 107- 108 C./0.3 mm. The yield was 77.5%of theory.

Example 5.N,N,N,N'-tetracyclohexyl ethylene diamine 543 g. (3.0 mol) ofdicyclohexylamine were boiled under reflux conditions and 51 g. (0.15mol) of 1,2-di (benezenesulfonoxy) ethane in 500 cc. of dry dioxane wereadded to the boiling dicyclohexylamine over a period of 4 hours. Most ofthe amine (excess) was distilled off, 60 g. of sodium hydroxide in 300cc. of water added and the distillation continued until a residualcloudy oil remained. This was poured into 200 cc. of Skellysolve (a lowboiling saturated hydrocarbon B. P. 41 69 C.), the mixture heated toboil, decolorizing charcoal added and the mixture filtered throughkieselguhr. The filtrate was then chilled to give white, needle-likecrystals having a melting point of 102 to 104 C. A yield of 85.9% oftheory was obtained.

ANALYSIS Calcu- Found lated Percent Percent droxide in 600 cc. of waterwas added to the residue. An oil layer separated. This was drawn ott andthe water layer extracted with several changes of benzene. The oil andbenzene solutions were combined, washed with water and dried over solidsodium hydroxide pellets. The oil and benzene solution was distilled upto 183 C./ 23 mm., and then the residual oil was fractionated through aglass packed column with a variable take-off head. The main cut wastaken off at 148 to 155 C./ .04 mm. On redistillation of the latter,there was obtained a yield of 64.8% of theory of N,N,N',N'-tetraphenyltrimethylene diamine, a yellow oil boiling at 1l8-121 C./0.3 mm.

ANALYSIS Calcu- Found lated Percent Percent C 85.3 85.7 7. 0 6. 9 7. U7. 4

Example 7.2,5- dimorpholino) hexane CH2-CH2 CH2-CH2' NCHCH2CHrCH-N CH2C2Ha Ha CH2C2 522 g. (6.0 mol) of morpholine and g. (0.3 mol) of 2,5-di(benzenesulfonoxy) hexane were heated together under reflux conditionsin a 2 liter, 2-necked flask, equipped with an 18" glass packed column,variable constant take-off still head and protected from moisture by acalcium chloride tube, for a period of 20 hours. The excess ofmorpholine was distilled off, 40 g. of sodium hydroxide dissolved in 600cc. of water was added to the residue and the mixture stirred. The oilylayer which formed was separated and the water layer was extractedseveral times with benzene. The oil and benzene extract were combined,dried over sodium hydroxide pellets and then fractionally distilled. The2,5-(dimorpholino) hexane was obtained as a light yellow, viscous oil in66.5% of theory yield and having a boiling point of 132 C./ 0.3 mm.

Example 8.-N,N'-dipiperidyl pentamethylene diamine 850 g. (10 mol) ofpiperidine were heated to reflux temperature in a Z-necked flask,equipped with a column, a variable take-ofi still head and a droppingfunnel, and 130 g. (0.50 mol) of 1,5-di (methanesulfonoxy) pentane in1000 cc. of dry dioxane was added over a period of 4 hours. Most of thepiperidine (excess) was removed by distillation. Then 60 g. of sodiumhydroxide dissolved in 300 cc. of water were added and the distillationcontinued until all the low boiling substances had been removed. Themixture was cooled and the oily layer which separated was drawn off. Thewater layer was extracted with diethyl ether and the extract combinedwith the oil. The ether and oil were dried over sodium hydroxide pelletsand fractionated. The N,N'-dipiperidyl pentamethylene diamine wasobtained as a light yellow oil having a boiling point of 110 C./ 0.5 mm.The yield was 25 of theory ANALYSIS ANALYSIS Found 3 23 Found iigg' .i

5 Percent Percent Percent Perc C 15.4. 75.6 66.6 66. H 12.7 12.6 12.812. N a 11.9 11.7 13.1 12.

' By proceeding as described in the above exam les,' Example'(Dusopmpylammo) dlethyl ethe" other tetrasubstituted diamines can alsobe prepared in E excellent yields, For example, .N-methylaniline with lgt- 0H (3H di-(p-toluene sultonoxy) butane gives N,N'-dimethyl-N,N"-diphe'ny'l tetramethylene diamine and dibenzyl- C2H4OC2H4N aminewith, 1,5-di-(methanesulfonoxy) pentane gives' CH1 w 7 3N,N,N,N'-tetrabenzyl pentamethylene diamine.

CH CH What we claim is: v g 1. A process for preparing atetrasubstituted diamine 3 7 having the general formula: '606 g. (6.0mol) of diisopropylamine were placed ina i R 3 liter flask, equippedwith a glass packed column and CH variable take-ofii still head, astirrer (sealed), a dropping funnel and protected from external moistureby calcium R 1. chloride tubes, and heated to boiling temperature. Whilewherein n represents a positive integer of from 2 to 6 7 stirringvigorously, there were slowly added 121 g. (0.31 and each R represents amember selected from the group 11101) of B l Y) yl ether disconsistingof an alkyl group containing from 1 to 4 carsolved 500 cc. of drydioxane. The reaction mixture bon atoms, a cyclohexyl group and a phenylgroup, comwas stirred and refluxed for 20 hours. The excess of prisingheating at a temperature of from 50 to 150 C. p g fiy g a i116dioxflflfil removed y st l a glycol disulfonate having the, generalformula: tion. e resi ue was treated wit 20 g. of sodium hydroxide in600 cc. of water. An oily layer formed which R1 O SO2(c H2) SO,2 O R1was drawn off, The water layer was extracted with benwherein n has theabove meaning and R1 represents the zene. The oil and the benzeneextract were then comsame member selected from the group consisting ofan bined and dried over anhydrous potassium carbonate and. alkyl groupcontaining from 1 to 4 carbon atoms, a distilled twice through amodified Claisen flask. The phenyl group and a tolyl group, with asecondary amine p,fi'- (diisopropylamino) diethyl ether was obtained asa having the general formula: colorless oil in yield of 65% of theoryand having a boil- R ing point of 96.5 C./0.5 mm.

ANALYSIS 40 R wherein each R has the above meaning, in the ratio ofFound from 4 to. 25 mol weights of the secondary amine to' each molWeight of the ,saidglycol disulfonate, then add Percent Percent ing anaqueous solution of an alkali metal hydroxide to g"- 33-3 2 the reactionmixture in the ratio of from 2 to 15 mol 1 j weights of the alkali metalhydroxide to each mol weight I V of the said glycol disulfonate, andseparating the tetrasubstituted diamine which forms from the reactionmix- In place of the diisopropylamme in the above ex- I ample, there canbe substituted a molecularly equivalent A Process f preparing N N' u h 1h lamount methylphenylamme 5:l ene diamine comprising heating at atemperature of from phenylammq) methyl ethef or dlcyclohexylamme 9 50 to150 C. 1,2-di(benzenesulfonoxy) ethane with diw fi fi'- q e dlethyiether. or of ethylamine in the ratio of from 15 to 20 mol weights ofPhenylamme to glve filsqdlphenylammo) d1ethyl etherthe diethylamine toeach mol weight of the 1,2-di(benzenesulfonoxy) ethane, then adding anaqueous solution Example '(Dlethylammo) dlethyl ether of an alkali metalhydroxide to the reaction mixture in 01115 the ratio of from 2 to 15 molweights of the alkali metal NC2H4 O-'C2H4N hydroxide to each mol Weightof the 1,2-di(benzene- C2115 C2115 sulfonoxy) ethane, and separating theN,N,N',N-tetraethyl ethylene diamine which forms from the reaction 438g. (6.0 mol) of diethylamine and 128.6 g. (0.33 mixture. g mol) offiLpT-di-(benzenesulfonoxy) diethyl ether were 3. A process forpreparing N,N,N,Ntetraisopropyl heated andstirred together at refluxtemperature for a trimethylene diamine comprising heating at atemperature period of 4 hours. The excess diethylamine was removed offrom 50 to 150 C. 1,3-di(benzenesulfonoxy) propane. by distillation ofthe reaction mixture. There were then with diisopropylamine in the ratioof from 15' to 20 mol added to the residue 60 g. of sodium hydroxidedissolved weights of the diisopropylamine to each mol weight of in 300cc. of water. The oily layer which separated from thel,3-di(benzenesulfonoxy) propane, then adding an the mixture was drawn0E and the water layer extracted aqueous solution of an alkali metalhydroxide to the several times with diethyl ether. The oil and etherexreaction mixture in the ratio of from 2 to 15 mol weights tract werecombined, and dried over sodium hydroxide of the alkali metal hydroxideto each mol weight of the pellets. The ether was removed by distillationand the l,3-di(benzenesulfonoxy) propane, and separating thej' residualoil fractionated. The fi,;3-(diethylamino) di- N,N,N',N-tetraisopropyltrimethylene diamine which ethyl ether was obtained as a very lightyellow oil having forms from the reaction mixture. a boiling point of69-70/ 1 mm. The yield was 13% 4. A process for preparingN,N,N,N'-tetracyclohexyl of theory ethylene diamine comprising heatingat a temperature of coma;

from 50 to 150 C. 1,2-di(benzenesulfonoxy) ethane with dicyclohexylaminein the ratio of from 15 to 20 mol Weights of the dicyclohexylamine toeach mol weight ot the 1,2-di(benzenesulfonoxy) ethane, then adding anaqueous solution of an alkali metal hydroxide to the reaction mixture inthe ratio of from 2 to 15 mol weights of-the alkali metal hydroxide toeach mol weight of the l,2-di(benzenesulfonoxy) ethane, and separatingthe N,N,N,N'-tetracyc1ohexyl ethylene diamine which forms from thereaction mixture.

5. A process for preparing N,N,N',N'-tetraethyl ethylene diaminecomprising heating at a temperature of from 50 C. to 150 C.1,2-di(benzenesulfonoxy) ethane with diethylamine in the ratio of from15 to 20 mol weights of the diethylamine to each mol Weight of the1,2-di(benzenesulfonoxy) ethane, then adding an aqueous solution of analkali metal hydroxide to the reaction mixture in the ratio of from 5 tomol weights of the alkali metal hydroxide to each mol weight of the1,2-di(benzenesulfonoxy) ethane, and separating the N,N,N'N'-tetraethylethylene diamine which forms from the reaction mixture.

6. A process for preparing N,N,N,N-tetra-n-butyltetramethylene diaminecomprising heating at a temperature of from 50 to 150 C. 1,4-di(p-toluenesulfonoxy) butane with di-n-butylamine in the ratio of from tomol weights of the di-n-butylamine to each mol weight of the 1,4-di(p-toluenesulfonoxy)butane, then adding an aqueous solution of an alkalimetal hydroxide to the reaction mixture in the ratio of from 2 to 15 molweights of the alkali metal hydroxide to each mol weight of the1,4-di(p-toluenesulfonoxy) butane, and separating theN,N,N',N'-tetra-n-buty1 tetramethylene diamine which forms the reactionmixture.

7. A process for preparing N,N,N,N'-tetrapheny I trimethylene diaminecomprising heating at a temperature of from to C.1,3-di(benzenesu1fonoxy) propane with diphenylamine in the ratio of from15 to 20 mol weights of the diphenylamine to each mol weight of the1,3-di(benzenesulfonoxy) propane, then adding an aqueous solution of analkali metal hydroxide to the reaction mixture in the ratio of from 2 to15 mol weights of the alkali metal hydroxide to each mol weight of the1,3-di(benzenesulfonoxy) propane, and separating theN,N,N',N'-tetraphenyl trimethylene diamine which forms from the reactionmixture.

References Cited in the file of this patent UNITED STATES PATENTS2,261,002 Ritter Oct. 28, 1941 2,279,294 Hardman Apr. 14, 1942 2,464,199Elderfield et a1 Mar. 15, 1949 FOREIGN PATENTS 518,592 Great BritainMar. 1, 1940 536,017 Great Britain Apr. 30, 1941 OTHER REFERENCES Gilmanet al.: I. Am. Chem. Soc., vol. 47 (1925), p.249.

Anderson et al.: J. Am. Chem Soc., vol. 61 (1939), pp. 3440-1.

Degering et al.: An Outline of Org. Nitrogen Compounds (1945), p. 201.

1. A PROCESS FOR PREPARING A TETRASUBSTITUTED DIAMINE HAVING THE GENERALFORMULA: